Esters and method of producing the same



Patented Mar. 18, 1941 UNITED STATES ns'rrns AND METHOD OF PRGDUCING rmSAME Theodore F. Bradley, stamiordrand wllliam B.

Johnston, American Cyd a corporation oi Coma, assignors to mpany, NewYork, N. Y., Baa-inc g No Drawing. Appiimtion November 28, 1938,

. Serial No. 242,556

261 Claims.

This invention relates to mixed esters and to methods of producing thesame. It is particularly concerned with esters which may be described asesters of non-conjugated terpene-fumaric acid complexes, and methods ofproducing the same.

This application is a continuation in part of our copending applicationSerial No. 215,584., en-

titled Esters and methods of producing the same, filed June 24, 1938.

It is known that maleic anhydride will react with both conjugated andwith non-conjugated terpenes upon heating mixtures thereof at termperatures variously ranging from 40 C. to 226 C. Such reactionsgenerally result in the production of various unsaturated dibasic acidanhydrides of liquid, or less frequently crystalline or amorphous solidforms, together with lesser amounts of more complex resinous acidanhydrides of higher molecular weight and of higher degrees ofpolybasicity. In the production of these acid anhydrides according tothe usual processes, we have found that the ratio of dibasic to the morepolybasic fractions will vary according to the constitution andproportion of the terpene fractions employed and according to thereaction conditions, especially the temperature.

While some of the complex mixtures oi acid anhydrides of thismaleic-terpene prior art have beenesterified for the production of alkydresins and other esters, their use for many purposes, is somewhatlimited because of their inherent deiects. We have found, for example,that at elevated temperatures, including the range in which alkyd,poly-esters are normally prepared, certain of these acid anhydridesundergo decomposition, frequently with loss of carbon dioxide and othervolatile matter and in some cases with more drastic decomposition intovolatile hydrocarbons and succinio-anhydride.

It has been suggested that certain of these objections may be overcomeby the fractional vacuum distillation of the mixture of complex acidanhydrides of these terpene-maleic anhydride reactions, during which thedibaslc constituents are isolated and may thereafter be separatelyesterified. This necessarily creates a large amount of by-product forwhich some disposition must be found and increases the cost of thedesired product to a substantial extent. I

In the various processes described for the productionof reactionproducts of non-conjugated terpenes and maleic anhydride by heatingmixtures of the same, it has frequently been stated maleic anhydride andequivalent results obtained.

We have found the contrary to be true. We have found that mixtures offumaric acid and nonconjugated terpenes are substantially unreactivethroughout the suggested temperature ranges. Using suggested reactionconditions, even for long periods of time, we have found that fumaricacidof reaction with fumaric acid is observed. In

other words, we have found that fumaric acid does not react withthenon-conjugated terpenes under the conditions described as suitablefor maleic anhydride and alleged to be suitable for fumaric acid. r

These statements of the equivalency of fumaric and maleic acids areapparently based on the assumption that fumaric acid is allegedlyconverted to maleic anhydride at elevated temperatures. However, we havefound that upon heating fumaric acid for eleven hours at 200 C., no

detectable amount of maleic acid or anhydride is formed. Likewise, uponheating fumaric acid at 250 C. for eleven hours, the fumaric acid ispartially decomposed with evolution of carbon dioxide and less than 0.25per cent of maleic acid is formed. Since these temperatures are abovethose generally suggested for reaction with the terpenes, the allegedrearrangement of fumaric acid to maleic anhydride or maleic acid couldnot be substantiated. 1 v

ldialeic anhydride reacts exothermically with conjugated terpenes andthese reactions may be brought about at temperatures even below C.Maleic anhydride combines quickly and readily with non-conjugatedterpenes at the reflux temperature of l70-180 C. The results obtainedwhen fumaric acid is heated with terpenes, are

quite different. Fumaric acid will combine slowrefluxing mixtures of thesame at l70-190 C.-

for several hours. The resulting products are resinous acids differingin many respects from the corresponding maleic anhydride reactionproducts.

One of the objects of the present invention is to provide a meanswhereby the inactivity of fumaric acid toward the non-conjugated.terpene hydrocarbons may be overcome andthus an entirely new and usefulseries of derivatives made available for industrial purposes.

It is another object of the present invention to provide a process bywhich the materials employed may be readily and efllciently reacted toproduce directly an alkyd-poly-ester mixture relatively free fromundesirable polybasic components.

These and other objects are attained by causing the iumaric acid tocombine chemically with non-conjugated terpenes of the CioHae series,using solubilizlng and reactive alcohols to produce esters ofcomplex'organic acids which are formed during reactions that apparentlyinvolve the unsaturation of both the terpene and the fumaric acid andare produced solely as eaterified derivatives by our methods ashereinafter described. We have found that ii fuma-ric acid be admixedwith an alcohol and one or more nonconjugated terpenes of the'CmHicgroup and the mixture be caused to react simultaneously, there averages180 6., results in the recovery of 45 parts by weight oi aqueousdistillate, 118 parts results chemical interaction of the iumaric acid,terpene, and alcohol, and esters of relatively low acid number areformed in high yields without objectionable side reactions ordecompositions.

The principles and practice oi our invention will be more clearlyunderstood by reierence to the examples given by way 01' illustrationand not in limitation. In each of the following examples, the stipulatedamounts of non-conjugated terpenes, alcohols and iumaric acid are placedin a suitablereaction vessel, and said vessel may be advantageous yequipped with an erficient mechanical agitating device, a thermometerwell and a side arm to which is attached a reflux condenser and a watertrap. Agitation is commenced in each case shortly after heating is begunand catalysts are introduced at this point in those examples wherecatalysts are employed. The temperature of each reaction mixture is heldcontinuously at the reflux point so that the excess of unreacted terpeneand the water of esteriflcation are distilled together, condensed andseparated, and the separated terpene is returned to the reactionmixture. In general, the reaction mixture is heated to about 170 C. andis then gradually increased to Ir'om 180 C. to 210 C.

The exact temperatures used in each specific case, however, areinitially subject to the boiling points of the reacting materials andgradually increase as the water of esteriflcation is eliminated. In allcases the reaction mixtures. are best refluxed until substantially allwater evolution has ceased. Following this, the excess or unreactedterpene is removed under reduced pressure and the resulting esters arerecovered for subsequent use.

Reaction of this mixture under the general conditions as described, fora period of 9 hours in which the temperature of .the reaction mixture byweight of uncombined terpene and about 392 parts by weight of a viscous,balsam-like polyester having an acid number of .0.

Example 2 Parts by weight Dipentene 400 Fumaric i 17.5 Triethyleneglycol Under the aforesaid conditions, after a reflux period of 6 hours,there is obtained 21.3 parts of aqueous distillate, 329 parts ofuncombined terpene and about 227 parts of a viscous, balsamlikepoly-ester having an acid number of 35.6.

Example 3 Parts by weight Dipentene 200 Fumaric acid Triethylene glycol200 Stannic chloride 5 This mixture (corresponding to Example 1 exceptfor the added catalyst) is found to react more vigorously so that duringrefluxing, the temperature rises to 200 C. and in two hours there areobtained 17.5 parts of aqueous distillate, 69 parts uncombined terpeneand about 443 parts of a viscous, balsam-like poly-ester having an acidnumber of 24.6.

Example 4 Example 5 Repetition of Example 3 using 5 parts of iodine inplace of stannic chloride yields, after refluxing for 4 hours at -2l0C., 45 parts of aqueous distillate, 54. parts of uncombined terpene andabout 461 parts of a balsam-like poly-ester having an acid number of55.2.

Example 6 Parts by weight Dipentene 300 Fumaric acid 155 Triethyleneglycol 260 Iodine 5 After 5 hours. refluxing at 180-200 0., there areobtained from this reaction 45 parts of aqueous distillate, 116 parts ofuncombined terpene and about 499-parts of a balsam-like poly-esterhaving an acid number of 61.5.

Example 7 I Parts by weight Dipentene 250 Fumaric acid 78 Triethyleneglycol- 100 Glycer 111 Linseed fatty acids 93 Stannic chloride 1.2

After 8 hours of refluxing at ISO- 0., there are recovered 33 parts oraqueous distillate, 162 parts of uncombined terpene and about 338 partsof an oxygen-convertible, balsam-like poly-ester having'an acid numberof 18.

After 5 hours of refluxing while the temperature is gradually raisedirom 170' C. to a maximum of 230 0., there are obtained 24 parts ofaqueous distillate, 35 parts of uncombined terpene and about 345 partsof an oxygen-convertible. balsam-like poly-ester having an acid numberExample 9 Parts by weight Dlpentene 182 Fumaric acid 116 Ethylene gly 62Linseed on 14'! Stannic chloride 1.8

After 3% hours of refluxing while the temperature is raised to a maximumof 210 0., there are obtained 39 parts of aqueous distillate, 74 partsof uncombined terpeneand about 395 of a plastic, ozqgen-convertibleresin having an acid number of 25.8.

After 5 hours of refluxing i temperature reaches a .51 of 195: 0., thereare obtained 27 parts of aqueous distillate, 46 parts of uneombinedterpene and about 1'13 parts of a hard resin having an acid number of64.2.

Example 11 Parts by weisht Dipentene Glycerol alpha monophenyl ether-"s7 Fumaric acid 33 Stannic chloride 0.5

After 5% hours refluxing at 180-19c 0., there are obtained 9.5 parts ofaqueous distillate, 76 parts of uncombined terpene and about 95 parts ofa hard resin having an acid number of 47.4.

Example 12 rts by weight Dipenten 1 Glycerol alpha monomethyl ether 53Fumaric acid 58 Stannic chloride 1 After 3 /2 hours refluxing at mo-19o" c... there are obtained 25 partsof aqueous r 7 parts of uncombinedterpene and abcutiw parts of a hard ester resin.

Example 13 v Parts by, weight Alpha pinen 150 Triethylene glycol liloFumaric acid -1 Z8 After 5 /2 hours refluxing at ism-its" 0., there areobtained 22 parts of aqueous parts of uncombined terpene and about 261parts number of 49.

trample 8 I 7 Example 14 Parts by weight Partsby weight Dipentene Alphapinene rumaric acid l8 Triethylene glycol 100 I Triethylene glycol 100Fumaric acid l8 Linseed oi 98 Stannic chloride.... 1.2 Stannic chloride1.2

After 3 hours refluxing at -200' 0., there are obtained 24 p of aqueousdistillate. 28 parts of uncombined rpene and about 277 parts 0? aviscous balsam having an acid number 0 53.1.

This product is found to be convertible to an iniusible varnish-like minwhen its solutions in the monoethyl ether of ethylene glycol(Cellosolve) are applied to metal and stoved at 140 C. for 7 hour. Thehardness of these films is considerably increased when the solutions areadmixed with small amounts of cobalt naphthenate.

Example 15 Parts by weight Commercial octadecsnediol containing 10- 15%stearyl alcohol. 158 'Fumaric aci 58 Alpha pinen 100 Stannic chloride 1Aiter ii hours refluxing at ire-219 0., there are obtained 16 parts oiaqueous distillate, 51 parts 01 uncombined terpene and about 250 partsof a balsam having an acid number of 1.2.8.

Example 16 Parts by weight Alpha pinen 125 Amyl alcohol (Pentasol'jl 250Fumaric acid '78 Stannlc chloride 3 1. 17 parts: 7.0% boiling at lessthan 2. 85'parts= 35.0% boiling at 130 C. to

3. 108 parts= at 180 C. to

ei.4% boiling I C. 4. 33 parts= 13.6% liquid residue.

Total 243 parts=1iiil-0% Upon neutralization and repeated fractionationthere are obtained from these original fractions, liquid esters asifollows:

Fraction Boltingmnge zlgiezigsi I Rezi irglex 0c 130-140 0.0622 1.4501ems-20o 0.9m 1.4878 o esaoo 0.9m 1.4740

Example 17 .7 Parts by weight Dipentene ,612 n-Butanol 500 Fumaric acid348 Stannic chloritle-riioizanate 16.2

4- aasaose This is reacted for 18.5 hours under the condl- J tionsdescribed in Example 16, beginning at 120 C. and gradually increasing to105 C. as the water 01' esterification is eliminated. When the .reactionproduct is distilled at between 1-2 mm.

(mercury) pressure, 115 parts of aqueous distillate is first given 011and the following additional fractions are obtained:

Fraction Boiling range 1-2 mm.

Less than 100 C Undistillcd residue.. 39

Redistillation oi fractions (b) to (9), inclusive. gives the following:

Fractions 4 to 6, inclusive, werefound on analysis to contain theterpene adducts, and the following constants were found:

Density Refractive Acid 24/15.5O.| index we. No.

4 1.0050 1. 4704 14. 1 5 1. 0009 1. 4m 0. s 45- e 1.0050 1.4806 as Thestannic chloride-dioxanate catalyst used in this example is prepared byagitation of a 50 mixture of 350 parts by weight of dioxane with 250parts by weight of petroleum ether to which are slowly added 461 partsby weight of anhydrous stannic chloride in 100 parts oi petroleum ether.The reaction is exothermic and should be 55 kept below 30 C. by cooling.After the reaction has been eflected, the product crystallizes fromsolution upon cooling and is recovered as a white solid which is stableat room temperature in air. This product is particularly well suited asacatalyst forthe purposes of this invention.

Example 18 Parts by weight 65 Beta pinene 170 Glycerol 32 Triethyleneglycol '78 Fumaric acid 116 Stannic chloride-dioxanate 5 After 1% hoursrefluxing at 190 C., 58 parts by weight of uncombined terpene is removedby vacuum distillation and the resinous product remaining is aplasticsolid which is soluble in 78 toluene.

Example 19 Parts by weight Fumaric acid 116 Triethylene glycol 142 5Glycerol 4 Beta pinene- 170 Stannic chloride-dioxanate 3 A mixturecontaining these ingredients is heated to 180 C. in about one hour, to210 C. 10 in two hours, and then to 230 C. in a hali. hour. About 1 molof terpene combines with 1 mol of Iumaric acid. The acid number is about13-19.

A 60% solution in mineral spirits has viscosity F and color 6-7(Gardner-Holdt scales). 15

This resin at a ratio oi 5 parts to 1 part 0! /z second viscositynitrocellulose dissolved in a suitable solvent gave films whichair-dried tack tree. 2:1 mixtures are suitable as flexible adhesives.

Example 20 I Parts by weight Fumaric acid "1'16 Triethylene glycol 150Beta pinene 170 p-Toluene sulfonic acid 2 This mixture is heated to 180C. in about 4 minutes and to 200 C. in about minutes. After removing theexcess pinene by vacuum 30 distillation, a light colored resin'isobtained having about 1 mol of pinene combined per mol of fumaric acid.

Example 21 Parts by weight Fumaric acid 280 Glycerol 260 Beta pinene 328p-Toluene sulfonic acid. 0.6 40

This composition is heated to 170 C. in about 75 minutes when themixture becomes clear.

After 1 hour at 170 C., the excess terpene is removed by distillation,leaving a product having about -1 mol of terpene combined per mol offumaric acid. To about 583 parts of the product, a mixture containingabout 292 parts of linseed oil acids and 262 parts of pinene is added.The temmrature is raised to about l80-190 C. in 1 hour and heating iscontinued in this range for about 7-8 hours. The excess of terpene isremoved under' vacuum and the residue dissolved in mineral spirits toform a 50% solution. The acid number of the resin is about 10, the colorof the solution is about 4-5 and the viscosity of the solution is aboutN (Gardner-Holdt scales). Films from a similar solution of viscosity L(Gardner-mint), containing 0.04% cobalt naphthenate (Nuodex) air drydust-free in about 1 hour and tack-free in about 2 hours.

Example 22 Parts by weight Fumaric acid 232 5 Glycerol 160 Beta pin n I340 p-Toluenesulionic acid 0.4

This mixture-is heated to 7 170 C. in about 45 minutes and thetemperature maintained for about 30 minutes, or until clear. A mixtureof parts linseed oil acids and parts beta pinene is preheated to 160 C.and added to the first mixture which is maintained at C. This quantityof linseed oil acids is equivalent to about 75 20% of linseed Oil. at190-200 C. about 140 parts of linseed oil, the concentration of oilcombined with the resin is brought to about 35%.

If 900 parts of this product are dissolved in about 580 parts of mineralspirits, the resulting solution (containing about 50% of the poly-esterresin) has a viscosity about U and color about 5 This is heated about 3hours (Gardner-Holdt scales). The resin has an acid number of about 35.

Example 23 7 Parts by I weight 'Fumaric acid. 232 Glycerol 180 Beta.pinene 3&0 p-Toluene sulionic acid 0.4

The reaction is carried out in the same manner I as'in Example 22,adding the same amounts of oil acids, oil, solvent, etc. acid numberabout 21 and the solution, a viscosity of about Z3 about 4GaLrdner-Holdt scales).

lJitampZe 24 v Parts by weight Fumaric acid 116 Glycerol 00 Beta pinene170 p-Toluene sulionic acid 0.2

This composition is heated under an atmosphere of C0: to 170-l80 C. inabout 2 hours, or until the solution is clear, and'to this a mixture of70 parts linseed oil acids and 80 parts of beta pinene, preheated to 160C., is added. Heating is longer.

* Example 25 Parts by weight Fumaric acid 116 Glycerol I 80 Beta pinenel 170 p-Toluene sulfonic acid 0.2

The above composition is heated to 210 C. in about 15 minutes and thistemperature maintained for about '75 minutes. A mixture of '70 partssoya bean fatty acids and parts beta pinene is added. The mixture isheated for about 4 hours at 190-195 C. and the excess terpene removedunder vacuum. About 0.9 mol oi terpene per mol of fumaric acid was foundto have combined. A pale yellow, hard solid having some coldflow, withan acid number about 39.0 is obtained. The softening point by the ringand ball method is about 77 C. This resin is suitable for cooking withoils for varnish manufacture.

Upon the further addition of The resulting resin has an Example 26 lParts by V weight Fumaric acid 58 Glycerol 50 Benzoic acid 61 DipenteneStannic chloride 1 This mixture is heated about 3 hours at about 180(2., the resulting resin having about 1.1 mols of dipentene per mol ofiumaric acid combined. 7

Example 27 Parts by ,7 a weight Fumaric acid 58 Glycerol (95%): 4'7Diipentene 10c Rosin 150 Stannic chloride-dioxanate-- 1.35

The mixture is heated to about C. in about 20 minutes, then to 190 C. inabout 1 hour and maintained at 190-200 C. for about 45 minutes.

A hard, somewhat brittle product is obtained.

Example 28 Parts by weight Fumaric acid as Glycerol 48 Beta pinene.. 85Stannic chloride-dioxanate 2.?

This composition is heated to about 170-185 C. in about 1 /2 hours. Theheating is continued until the mixture clears, and then about parts ofrosin are added. After heating for about 1 hour at 180 C., a hard resinis obtained.

Example 29 Parts by weight Fumaric acid 116 tol 182 Beta pinene 170Stannic chloride-dioxanate 5 The mixture is heated to about 170 C. inabout 3 hours and the temperature maintained for about 1 hour. A clear,somewhat brittle, redbrown resin is obtained.

Example 30 Parts by weight Fumaric acid... 116 Polyglycerol (acetylnumber= 1070) 214 Betapinene 170 Stanmc chloride-dioxanate 5 Thismixture is heated to about C. in about 1 khours and then heated about 2hours at about C. A rubbery, relatively dark resin was produced havingabout 0.6 mol of terpene per mol of fumaric acid combined.

This composition is heated to about C. in about 1 hour and then at aboutC. for about 2 hours. A flexible typ of.resin is obtained.

The examples set forth above show typical &

methods of simultaneously reacting fumaric acid, a non-conjugatedterpene of the Ciel-lie series and a reactive solubilizing alcohol toobtain a wide variety of alkyd-poly-esters. Some of the examples showthe use of representative modifying 4 agents, e. g. drying oil acids anddrying oils.

. Characteristic of the products of this invention is the substantialabsence of esters of acids having a polybasiclty greater than two,wherefore the viscosities and softening points tend to be lower than themaleic-terpene esters of the prior art. Fractionation of the butyl andamyl esters of the terpene-furmaric adducts of the present invention hasalso shown that far larger proportions oi these are distillable than inthe case of the butyl and amyl esters of the two stage maleic-terpeneadducts.- These differences may be attributable to the absence of suchsubstantial amounts oi polymeric apids as have been found tocharacterize the terpene-maleic adducts of the prior art.

By suitable regulation of the reaction conditions we may vary thecombining ratio of terpene to fumaric acid and consequently of theproportion the various esters produced within considerable limits and byvarying the solubilizing and reactive alcohols used we can produce alarge number of newand useful derivatives.

The reactive solubilizing alcohols suitable for the practice of thisinvention are those which contain non-acidic primary or secondaryhydroxyl groups and which are generally capable of esterification. Ithas been found possible also to employ other compounds of an alcoholicnature, such as the polyglycols, polyglycerols, mono aryl or alkylethers ofglycerol, and the like. Various mixtures of alcohols may beused, especially mixtures of alcohols containing diiierent numbers ofhydroxyl groups, 'e. g., a monohydric alcohol with a dihydric alcohol, amonohydric or dihydric alcohol with a higher polyhdric alcohol such asglycerol, etc.

Monohydric alcohols yield, in general, analogous but liquid esters ofvarying boiling range while the polyhydrlc alcohols generally yieldbalsamlike or solid resins.

The higher polyhydric alcohols, l. e., those containing three or morehydroxyl groups, tend to react with the fumaric acid to yield insolublegels without effecting suflicient combination of the terpenes. Thistendency may be largely overcome by the use of an excess of the alcohol,by the use of suitable catalyst, and by carefully controlling thetemperature to avoid overheating, particularly in the early stage ofthereaction. The temperature should be raised only very slowly to about170-180 C. After tlfe'reaction has proceeded until the mixture is clear,the reaction temperature may be raised to 180-200 C. With the highertemperatures, however, premature gelation is most likely-to occur.

In order to obtain products of particular commercial utility, we havefound it desirable to modify some of the cdmpositions, and especiallythe glycerol-fumaric-terpene products in various ways in order to obtainresins having certain desirable properties. In general our terpeneesters are more readily soluble in hydrocarbons than the phthalate typesof alkyd resins. By slight modification of our resins it is possible to.obtain resins having a high degree of oil solubility, quick airdryingproperties, etc. .One way of obtaining improved oil soluble resins is toincorporate small amounts of fatty oil acids in the composition afterthe initial reaction of the mixture including an alcohol (e. g.glycerol), terpene, and furnaric acid.

aaaaosa Alter initial reaction has taken place, i. e. when thereactionmixture becomes clear, about or more of fatty oil acids (calculated astriglyceride) e. g. linseed oil acids, are added to the mixture. It isespecially important that the iumaric acid and terpene should becombined before the addition of any conjugated fatty oil acids in orderto avoid reaction between the fumaric acid and the conjugated iatty oilacids before the terpene has had sumcient time to combine. It has beenfound advantageous in some cases to preheat the fatty oil acids beforeadding to the reaction mixture.

if more. than about 20% of fatty oil be desired in the final product, itmay be added during the latter stages of reaction in the form of eitherfatty oil acids or as'the oil itself, as desired. Since the oil is lessexpensive than the acids it will usually be preferable to add the oilitself rather than the acids. The addition of about 20% of fatty oilacids (calculated as triglyceride) in the early stage of the reactioncauses the composition to become miscible with additional oil aftersuitable reaction. Accordingly large amounts of the corresponding fattyoil or other fatty oils may be added to the, composition if thetemperature be kept relatively high, e, g. about 170 C.

When the resin is to be modified with fatty oil acids, additionalalcohol, equivalent to the fatty oil acids to be added is usually addedto the original mixture of fumaric acid, terpene and alcohol.

Our resins may be modified with any of the fatty oils. Examples ofsuitable fatty oils are: tung, soya bean, perilla, rapeseed, cottonseed,olein, 'stearin, etc. It may be desirable to modify the resin withdrying oil acids and a drying oil, particularly if the resin is to beused in airdrylng coating compositions. For this purpose we have foundthat linseed oil and linseed oil fatty acids are especially suitable.The term drying oil is intended to include semi-drying oils as well asthe strictly drying oils. Obviously various mixtures of fatty oils orfatty oil acids may be used. The resins produced by modification withfatty oils are usually quite soluble in hydrocarbon solvents. They are,therefore, particularly suitable for use in varnishes, lacquers, etc.

Another way in which the compositions of our invention may be modifiedin order to obtain oil soluble products is by the addition of suchsubstances as rosin acids, benzoic acid, etc., to the reaction mixture.If a conjugated compound such as rosin be used, this addition ispreferably after all, or nearly all, of the terpene has combined withthe fumaric acid as otherwise the modifying substance may combine withthe fumaric before the latter has time to combine with the terpene.

In operating our process, we have found it advisable, although notessential, to employ sumcient excess of the terpene over the combiningequivalent for the fumaric acid so that this exa of addition reactionand of esterification have been attained. In the operation of .ourprocess, it is sometimes possible and advantageous to employ inertvulatile diluents for the reaction mixture. Among materials suitable forthis purpose may be mentioned benzene, toluene, xylene, ethylenedichloride or the like in place of an excess of terpene.

We have also found it'possible to substitute a part of our terpenes witha corresponding amount of reactive non-terpene hydrocarbons and othervolatile and polymerizable unsaturated bodies as, for example, styrene,dicyclopentadiene, cumarone and indene and certain vinyl, acrylic andmethacrylic esters.

In the operation of this process, it has been found somewhat difilcultto combine more than an average of 55 mol of terpene to each moi offumaric acid unless a suitable catalyst be employed, although by the useof a large excess of terpene and by particular selection of the terpenesused, it has been ioimd possible to exceed this combining ratio. Ingeneral, however. when higher ratios of combined terpene are required,we prefer to use a catalyst. Suitable catalysts are included in thegroup of the halogens. hydrogen halides or metallic'halides and the useof such compounds is illustrated in some of the examples. Of the varioussubstances which have been found to catalyze these reactions, stannicchloride or stannic chloridedioxanate are particularly suitable. Otheracidic catalysts could be substituted and among these we have found thesulfonic acids particularly suitable, e. g., p-toluene sulfonic acid.

When dihydric alcohols are used in practicin our invention, we prefer toemploy only the theoretical equivalent of alcohol based on the amount offumaric acid used, althoughthe use of lesser or greater amounts ispermissible. If monohydric alcohols or those containing more than twohydroxyl groups are used, then we usually prefer to use an excess of thealcohol. An excess of about 20% has been found suitable when glycerol isused. The amount of alcohol used depends somewhat on the propertiesdsired in the resulting resin.

Terpenes suitable for the purpose of this invention are limited to thoseof the CioHis series which are of non-conjugated structure and amongwhich alpha and beta pinenes, the limonenes, dipentene, and terpinoleneare particularly suitable. It is found possible to-use gum terpentine orsteam distilled wood turpentine in place of alpha pinene or of othernonconjugated ierpenes with entirely satisfactory results. The use ofturpentine or of other distillates rich in pinene is especiallyadvantageous for economic reasons.

The products of this invention have been found to possess great utility.The liquid esters derived from the monohydric alcohols and thehydrogenated modifications of such esters have been found suitable foruse as plasticizers for nitrocellulose and in certain cases, for ethylcellulose or for other cellulose esters or ethers. Our poly-esters havealso been found to be useful. resins or resinous plasticizers forcellulose derivatives, particularly nitrocellulose. Many of thepoly-esters, with or without fatty acid or drying oil modification, havebeen found to be oxygen-convertible and of considerable utility inaim-drying or in stoving paints, varnishes and enamels.

Certain of the products such as those .prepared in accordance withExamples '7 and-8 have been found to yield superior binders for linoleumand related plastics. Products of the present invention are also usefulfor printingor lithographing inks, gaskets, cements or adhesives and forgeneral com or impregnating purposes.

Such other suitable changes and variations may be made in carrying outour process without departing from the spirit and scope of our inventionas defined in the appended claims.

.1. A process for the production of ester condensation products whichcomprises heating to reaction temperatures a mixture containing fumaricacid, a non-conjugated terpene of the CioHis series and a reactivesolubilizing alcohol.

2. A process for the production of ester condensation products whichcomprises heating to reaction temperatures a mixture containing fumaricacid, a non-conjugated terpene of the CmHu series and a reactivesolubilizing alcohol, the temperature, time and other conditions beingsuch as to bring about free and relatively continuous' voiatilizationand removal of water of condensation in adniixture with unreactedterpene.

3. Aprocess for the production of ester condensationproducts whichcomprises heating to reaction; temperatures a mixture containing iumaricacid, a non-conjugated terpene of the Cums-series and'a reactivesolubilizing alcohol, the temperature, time and other conditions ofreaction being such as to bring about free and relatively continuousvolatilization and removal of 'water of condensation in admixture withunreacted terpene. separating the water from the admixture and returningthe terpene to the reaction.

4 A process for the production of ester condensation-products whichcomprises heating a mixture containing fumaric acid, a reactivesolubilizing alcohol and a terpene distillate, the major portion ofwhich consists of non-conjugated terpenes of the ClOHlfi series, saidheating being continued at a temperature and for a time sumcient tobring about chemical combination of the mixture.

5. A process for the production of ester condensation products whichcomprises heating to reaction temperatures a mixture containing fumaricacid, a reactive solubilizing alcohol, and a non-conjugated terpene ofthe CmHm series in the presence of a catalyst selected from the groupconsisting of halogens, hydrogen halides, metal halides, and sulfonlcacids.

6. The process of claim 5 wherein the substance which catalyzes thereaction is p-toluene sulfonlc acid.

'I. The process of claim 5 wherein the substance which catalyzes thereaction is stannic chloridedioxanate.

8. The process of claim 5 wherein the alcohol is glycerol.

10. The process of claim 9 wherein the alcohol is glycerol.

11. The process of claim 9 wherein the fatty oil acids are linseed oilacids.

12. A process for the production of ester condensation products whichcomprises heating to reaction temperatures a mixture containing fumaricacid, a non-conjugated terpene of the CioHm series, and a reactivesolubilizing alcohol in the presence or a catalyst selected from thegroup consisting of halogens, hydrogen halides, metal halides, andsulfonic acids, continuing said heating until the reaction mixturebecomes clear, adding a mixture containing fatty oil acids and a solventtherefor to the reaction mixture and continuing heating until ahomogeneous product is obtained.

13. A process for the production of ester condensation products whichcomprises heating to reaction temperature a mixture containing fumaricacid, a non-conjugated terpene of the CioHm series, and a reactivesolubilizing alcohol in the presence of a. catalyst selected from thegroup consisting of halogens, hydrogen halides, metal halides. andsulfonic acids, continuing said heating until the reaction'mixturebecomes clear, adding a mixture containing fatty oil acids and a solventtherefor to the reaction mixture, continuing said heating until thereaction mixture is homogeneous and subsequently mixing therewith afatty oil.

14. A process for the production of ester condensation products whichcomprises heating to reaction temperatures a mixture containing fumaricacid, a non-coniugated terpene of the CmHrs series and glycerol in thepresence of a catalyst selected from the group consisting of halogens,hydrogen halides, metal halides, and

sulfonic acids, continuing said heating until the reaction mixturebecomes clear, adding rosin, and continuing said heating to give ahomogeneous product.

15. A process for the production of ester condensation products whichcomprises heating to reaction temperatures a mixture containing fumaricacid, benzoic acid, a non-conjugated terpene of the CmHu series andglycerol in the presence of a catalyst selected from the consisting oihalogens, hydrogen halides, halides, and sulfonic acids.

16. A compositionof matter comprising essentially a simultaneousreaction product of a. mixture containing ltumaric acid, anon-conjugated 1 terpene of the CmHis series and glycerol.

17. A composition at matter comprising essentially a simultaneousreaction product of fumaric acid, a non-conjugated terpene or the C1oH1sseries and an alcohol. 1

-18. A composition of matter comprising essentially a simultaneousreaction product of fumaric acid, plnene and an alcohol.

19. A composition of matter comprising essentially fatty acids derivedfrom a natural glyceride ester combined with the simultaneous reactionproduct of a mixture containing fumaric acid, a non-conjugated terpeneof the CroHm series and an alcohol.

20. A composition 01. matter comprising essentially a simultaneousreaction product or a mixture containing mmaric acid, glycerol and aterpene distillate, the major portion of which consists of pinene,modified with at least one substance selected trom the group consistingof linseed oil fatty acids and linseed oil.

THEODORE F. BRADLEY.

WILLIAM B. JOHNSTON.

group 1 metal I 7 CERTIFICATE OF comm-anon; Patent no, 2,25h,9 s.' 77March 18, 19141..

THEODORE F. BRADIEY,.ET AL.

It is hereby certified that error appears in the printed specification'of the above numbered patent requiring correction is follows: Page 5,first colmnn, line '59 for 'terpene" read --terpenes--; page 5, firstcolumn,

line 25, for a boutnh. Gardner-Bout read ---and color about I; (Gardner-Ho1dt--; page 6, first col'mnn, line 13, for "terpene-furmaric" read--terpene-fumaric--;' line 1 0, for "polyhdric" read 1 h dr1'c--;andthfit the said LettersPqtent should be read with this correctiontherein that the same may conform to the record of the case in thePatentofiice. Signed and sealed vthis 8th day of April, A. D. 19141.

, Her 1 ry Van Arsdale, .(Seal) Acting Commissioner of Patents.

